Bactericidal composition comprising tetra alkyl quaternary ammonium halide and hydrogen peroxide



BACTERICIDAL COMPOSITION COMPRISING TETRA ALKYL QUATERNARY AMMONIUM HALIDE AND HYDROGEN PEROXIDE Donald 0. Hitzman, Bartlesville, kla., assignor to Phillips Petroleum Company, a corporation of Delaware No Drawing. Application January 3, 1956 Serial No. 556,797

6 Claims. (Cl. 167-22) This invention relates to bactericides. In one aspect it relates to bactericidal compounds which are effective when added to water. In another aspect it relates to water containing the selected bactericides in effective amounts, which water is useful for many purposes requiring water in which bacteria do not multiply. In another aspect it relates to the use of such water for the recovery of oil from oil sands by displacing the oil with said water.

Bactericides for use in water to produce sterile water, or water in which bacteria, microbes, fungi, yeasts, and other like microorganisms will not multiply, are useful in many commercial applications. They are especially useful in the art of producing oil, and/or gas, from earth formations containing the same, by displacing the same with water. In these well operations it has been found Very difiicult to maintain the process if sulfate reducing and/or other anaerobic bacteria are present in the water employed.

The success, or failure, of a water flood of an earth formation may rest on the ability of the operator to control the growth of sulfate reducing bacteria in his injection water. These organisms cause corrosion of the well pipe by accelerating galvanic corrosion. Still more serious is their ability to rapidly reduce sulfates present in the injection water to sulfides, which react with the soluble iron salts in the water to form insoluble iron sulfide, which causes serious plugging of the formation into which the water is being injected.

Considerable efforts have been made in the prior art to control such bacteria and other microorganisms in the water used for these purposes, but the amounts of bactericide necessary have been excessive from an economical standpoint, and the effectiveness of the proposed bactericides has been poor, especially as to sulfate reducing bacteria. 7

It has now been discovered that when small amounts of selected bactericides, named below, are used in water together with a small but synergistic adjuvant amount of hydrogen peroxide, that these bactericides become highly useful, and very effective, in the practice of the present invention, for killing all types of bacteria, microbes, fungi, yeast, and other like microorganisms, especially those found in well water, especially sulfate reducing and/or other anaerobic bacteria which successfully resists large amounts of the bactericides of the prior art.

One object of. the present invention is to provide a novel additive for water for killing, reducing the number of and/ or inhibiting the growth of bacteria in water.

Another object is to providea novel aqueous liquid compound resistant to bacteria, and the like, comprising water and said additive.

Another object is to provide novel processes of treating wells with such water containing said additive.

Another object is to provide processes for producing oil and/or gas from sands containing the same by displacement by such water containing said additive, by wa- 2,917,428 Patented Dec.'15, 19 59 ter drive, water flooding, and/or repressuring such formations with such water.

Numerous other objects and advantages will be apparent to those skilled in the art upon reading the ac companying specification and claims.

It is proposed to produce water for commercial purposes by adding a selected bactericide named below, together with small but synergistic adjuvant amount of hydrogen peroxide. One process in which this water may be employed is in treating wells, such as washing the same with said water, or injecting the water into the permeable earth formations in the same which will accept water under pressure.

Furthermore, it is proposed to produce oil, and/ or gas, where these hydrocarbons are found occurring in pervious earth formations either being found there naturally, or being stored there by artificial underground storage processes, by displacing the same with said water resistant to the growth of bacteria. This displacement may occur in several ways, either horizontally or vertically. In the case of horizontal displacement water is forced down an input well into the formation displacing the hydrocarbon into an output well spaced from the input well, from which the hydrocarbon is removed. In the case of a vertical displacement the treated water is injected through a well into the lower part of the hydrocarbon containing formation, and the hydrocarbon is removed from the upper portion thereof either through the same well from which the water was injected, or through anotherwell, or wells, spaced therefrom.

All of these operations in wells are well known in the prior .art, but in the prior art it has been found that after a while the sulfate reducing and/or other anaerobic bacteria found in the water employed causes such corrosion of equipment, and plugging of formations, that th process becomes inoperative. Expensive cleaning out with acids and replacement of equipment then becomes necessary before the process can be resumed, and even when resumed is never as effective as at the start. By inhibiting the growth of such bacteria by the practice of the present invention a new process is produced which may be continued indefinitely without cleanout with acids, or replacement of equipment.

The selected bactericides which are useful and effective in the practice of thepresent invention, for killing all.

types of bacteria, microbes, fungi, yeasts, and other like microorganisms, especially those found in well Water, but especially for killing sulfate reducing and/or other anaerobic bacteria often found in water employed for oil recovery by water drive, or repressuring oil formations with water, are those consisting essentially of a small but bactericidal amount, preferably from 1 to 1,000 ppm. (parts per million), based on the volume of water to which it is added, of a bactericide selected from the group consisting of water dispersible and water soluble polyphenols, aliphatic polyphenols, salts of said phenols, and halogenated derivatives of said phenols and salts, alkyl quaternary ammonium salts, aliphatic amines, and salts of aliphatic amines, together with a small but synergistic adjuvant amount, preferably from 1 to 1,000 p.p.m., based on said volume of water, of hydrogen peroxide. The length of the aliphatic, or alkyl, radicals is most accurately defined, and most easily determined by those practicing the invention, as that giving a water dispersible or water soluble material, and it has been found that such is the case when these radicals have 20 carbon atoms or less, those with 5 to 20 being preferred.

The lower limitof 1 ppm. is effective in the practice of the invention when the bacterial count in the water to be treated is quite low, and can be employed when the water is substantially free of bacteria. The upper limit of 1,000 p.p.m. is set by economic considerations, as

much smaller concentrations will kill the bacteria. As shown by data below 10 p.p.m. of hydrogen peroxide and 20 p.p.m. of one of the selected groups of bactericides is quite effective in mostinstances, and in: commercial prac- Of these alkyl quaternary ammonium salts, those having from 5 to ZO'carbon atoms in the alkyl group. or in each alkyl group, as the case may be, are especially effective in this invention. The term alkyl quaternary tice it would almost never be necessary to use more than 6 ammonium salt covers both alkyl and dialkyl salts and 100 ppm. of both. mixtures of the same, as most Arquads are mixtures. Specific examplesof polyphenols useful in the inven- The alkyl radical may be paraffinic, olefinic, diolefimc, tion of the preceding paragraph are his phenol, tris phenol acetylinic, or otherwise unsaturated. and chlorinated or other halogenated bis phenols and tris For examples, dioctyl dimethylammonium chloride, phenols such as 2,2' methylene bis-4echlorophenol, sodi- 10 didodecyl dimethylammonium chloride, dodecyl trium pentachlorophenate and 2,2'-methylene bis-4-bromomethylammonium chloride, dihexadecyl dlmethylammoniphenol. A polyphenol salt containing compound useful um chloride, hexadecyl trimethylammonium chloride, in said invention is ET-S a bactericide made by Dow dioctadecyl dimethylammonium chloride, octadecyl tri- ChemicalCo., which is a liquid containing approximately methylammonium chloride, dioctadecenyl dimethylam- I 55% sodium salts of the reaction products between formmonium chloride, dioctadecadienyl dimethylammoniurn aldehyde and monoc-hlorinated phenols, therefore conchloride, hexadecyl octadecyl dimethylammonium chlosisting essentially of, and having as its principal active ride, octadecynyl trimethylammonium bromide, hexaingredient said 2,2-methylene bis-4-chlorophe'nol. Andecynyl trimethylammonium iodide, and octyl trimethylother polyphenol salt containing compound useful in this ammonium fluoride, and mixtures of the same are all useinvention is Dowicide F a bactericide made by the same 'ful in this invention. Other water dispersible salts, such company as a 34% solution of sodium pentachlorophenate as the acetates, sulfates, nitrates, and phosphates, are in ethylene glycol havinglthe former as the active ingredieffective in place of the chlorides, but the chlorides are cut. Bis phenol and tris phenol are obtainable from the preferred.

TABLE I Arquads-Average composition Carbon "33 Groups Chain Length Arquad Arquad Arquad Arquad Arquad Arquad Around 12 16 is o s 20 2H Active Ingredient. 50% 60% 50% 50% 75% 75% NaCl (approx.) 1 1 1 1 1 1 1 Isopropanoi (appro 49 49 49 49 49 24 24 Form at. Room Temp Liquid Semi- Seml- Scmi- Semi- Liquid Soft Liquid Liquid Liquid Liquid Paste ammonium chlorides.

Alkyl trimethylammonium chloride l H-C-H Dlalky] dimethylammonium chloride All others are alkyl trim ethyl A mixture of 1 part tallow trimethylammonium chloride and 1 part di-coconut dimethyl ammonium chloride in a 50% solution in propanol known as Arquad T-ZC is very elfective in the invention.

Arquads l0, 16, C, S, 2C, ZHT, 2T, 25, S20 and TZC are effective in the invention, and are preferred.

Specific examples of aliphatic amines effective in this invention include aliphatic amines, for example decyl amine, dodecyl amine, tetradecyl amine, hexadecyl amine, octadecyl amine, octadecenyl amine, octadecadienyl amine, octadecenyl amine chloride, dodecyl amine bromide and dodecyl amine phosphate are effective in this invention, as are mixtures of the same; and aliphatic diamines and their water dispersible salts, such as the acetates, sulfates, nitrates, phosphates, and halogen salts, such as chlorides, bromides, iodides and fluorides, but the acetates and chlorides are preferred.

As examples of aliphatic amines, the Armacs made by Armour Chemical Division, which are effective in this invention, are acetate salts of aliphatic amines and may be represented as follows:

Preferably R represents an alkyl group ranging in length from 5 to 20 carbon atoms, and may be parafiinic, olefinic, diolefinic, acetylinic, or otherwise unsaturated.

Armac C, 14, 16 and 18 are effective in this invention H H H 11 and are preferred. Qecyl amine acetate. dodecyl amine l l; 1 1 l i; acetate, tetradecyl amine acetate, hexadecyl amine acetate, 1 l l H octade'cyl amine acetate, octadecenyl amine acetate, and H I R i octadecadienyl amine acetate, are effective in this inven- Alkyldiamme Dmlkyldamme Trialkyldamme tion, 'asare mixtures of the same.

The Armacs are generally mixtures of aliphatic amines as follows:

In the sets of formulas above R, R and R" are the same or different alkyl radicals which preferably have from 5 to carbon atoms.

TABLE II N o. of Carbon Atoms in Alkyl Group 'letra- Hexa- Oeta- Oeta- Octadeca- Hexyl, Ootyl, Decyl, Dodecyl, decyl, decyl, decyl, decenyl, dienyl, 6 8 10 12 14 16 18 18 M0n0- 18 Poly- Saturated Unsat. Unsat.

Armac 8 3 90 7 Armac 8D... 3 90 7 Armao 10--- 4 90 6 Armac 10D 4 90 6 Armac 12D 2 95 3 Armac 14 4 92 4 Armae 14D 4 92 4 Armac 16D 92 7 Armac 18 7 90 Arman 18D 7 90 Armac HT 72 Armac HTD 25 72 8 9 47 18 8 5 20 17 26 37 Arizona SD 20 17 26 37 As examples of aliphatic diamlnes, the Duomeens As a specific example of a water dispersible salt of an made by Armour Chemical Division, which are effective in this invention, are aliphatic diamines and may be represented as follows:

alkyldiamine efiective in this invention, fDuomeen T diacetate is preferred, and isthe quaternary-.diacetate salt of a tallow primary amine, having the formula:

H H H H RNCOCNH I l l l H-C-H HCH H H H H H N 1 Preferably the alkyl radical R contains from to 20 (|7 H carbon atoms. Duomeen C, S and T are effective in HO-H H-C-E H this invention, and are preferred, as are combinations of 40 the same with Arquad S. i I

The quaternary salts and other water dispersible salts of said Duorneens" are efiective in the invention. Aliphatic amines may be reacted with alkyl halides to form quaternary salts, as follows:-

II EHHH named chemical compounds, and has a synergistic ad- Alkyldmmme $335 juvant bactericidal effect independent of the concentral {fig tion of the original source of hydrogen peroxidcz, or thel presenceor a sence of the usual amounts of t e usua R N CwN OHa +3110] hydrogen peroxide stabilizing agents generally employed CH3 CH3 in commercial aqueous solutions of hydrogen peroxide quaternary salt acid water dispersible salts, such as the chloride, acetate, sul- I fate, bromide, nitrate and phosphate salts.

The term aliphatic amines includes alkyl amines, dialkyl amines and trialkyl amines and quaternary amines and their salts which are all effective in this invention.

In the preceding formula the alkyl radical R comprises in different molecules generally the octadecyl and hexadecyl radicals from tallows.

Hydrogen peroxide has the well known formula H 0 and either concentrated, or dilute, aqueous solutions of the same may be employed in the practice of this invention in the amounts claimed along with any of the above to preserve, and retard decomposition, of the same. Therefore, in commercial practice of this invention it is preferred to employ ordinary commercial aqueous solutions of 5% to 30% by weight hydrogen peroxide and they generally contain a litle acetanilide as a preservative. Tests with and without this amount of acetanilide in the hydrogen peroxide show such amounts of acetanilide have no effect on the synergistic effect of hydrogen peroxide in the present invention. In the following tests the hydrogen peroxide did not contain acetanilide, nor any other preservative, being a chemically pure grade of hydrogen peroxide aqueous solution, having the trade mark name Superoxol containing only 29% by weight hydrogen peroxide, less than 0.02% non-volatiles, and the remainder water. The non-volatiles are classified as lessthan:

They may be represented as follows: 001% $04 f e t 0.001% N RN-H RNR R-NR 0.001% Cl I v H RI! phosphate 0.005% mso,

7 None of these listed trace materials, nor all of them, in such small amounts, could have any appreciable bactericidal, or preservative effect, as is easily demonstrated by adding larger amounts of the same without apprecipensed into one ounce dropping bottles. The droppers are graduated in units of 0.1 milliliter. The bottles are then inoculated with a five day actively growing broth culture of sulfate reducing bacteria. The incoulum able effect. should be sufiicient to give a final count of 400,000 bac- One of the most significant facts brought out by the teria per milliliter in the bottle. This can again be defollowing data is that large amounts of p.p.m. or termined with a bacteria counter and phase microscope. greater of phenol alone, or hydrogen peroxide alone, or At intevals of 5, 10, and 30 minutes, 0.1 milliliter mixtures of phenol and hydrogen peroxide, had substan aliquots are removed from the bottles and added to tially no bactericidal effect against sulfate reducing bac- 10 tubes of nutrient. All work is carried out at 25 C. and teria even after long periods of time of 30 minutes or done in duplicate. The concentration of bactericide givmore. Therefore it is unexpected, and a synergistic ading a 100 percent kill at a given time interval is indicated juvant effect, that the addition of small amounts of hyby the absence of any black colonies in the tube of nutridrogen peroxide should greatly increase the bactericidal ent after incubation for two weeks at 25 C. In all effect of the selected group of materials disclosed herein. 15 tests, a series of controls should be run using 0.85 per- EXAMPLE" gent saline solution inoculated with sulfate reducing acter1a..

. In qrder to give an example 9 the effeCtWeneS-S of To determine whether or not a bactericide will be effecinvention a number of exper1mental runs have been tive in a given Water, the test described in the previous made and the data from the same reported in Table III paranraph is modified in the following manner The g f g t p hosen f t t b bactericide under test is made up with water from the u a e re 11cm? a ena were or es S 67 field rather than 0.85 percent saline solution. A strain cause these bacteria are the most difficult to control, and of sulfate reducing bacteria is used that has been the strains of bacteria employed were secured from wells lated from the Water to be treated The exposure time m Winch the most pluggmg condmons exlst' to the bactericide should be about the same as that to I The sulfate reducing bacteria chosen for the tests rebe used in the field that is 5 10 15 and minutes Table p i were taken from produced w which is about the time it takes the water to travel from water m a wilter mlectllm system? tladly troubled by mm the point of bactericide injection to the input well. Finally sulfide deposits from said bacteria 1n the North Burbank the test should be conducted at the temperature of the field. This well Water was used to inoculate a suitable 30 water in the field which is sometimes about 0 C when sulfate reducing bacteria culture medium, and the culused tured colonies used to inoculate the solution of bac- Tl'lis test is used for both fresh and produced waten tencldal P tested In Table III the sub-heading In the Burbank produced The solutions of various strengths of bactericidal comwell water means the solutions of various percentages Pounds bemg tested were made up Wlth elther some of 5 of bactericides were all made up with water produced said produced well Water from said North Burbank field, or with fresh water.

Various concentrations of the compound under test are made up in 0.85 percent saline solution, and disfrom the output wells of Water flood unit NBU-l38, a group of wells in the North'Burbank unit, in the North Burbank field, which produced water is a dilute brine favorable to the multiplication of sulfate reducing bacteria.

TABLE III Bactericidal Eflect AFTER 5 MINUTES (In the Burbank produced well water) Amount of compound used in p.p.m. and black bacterial colony count after time given 112m Bactericlde Compound 2.5 I 5 7.5 10 20 p.p.m p.p.m p.p.m p.p.m p.p.m

1, 000 1, 000 1,000 1, 000 1, 000 1, 000 1, 000 l. 000 1, 000 1. 000 1, 000 1, 000 1,000 1,000 1, 000 1. 000 1. 000 1, 000 28 (Tris phenol plus 10 p.p.m. H 0 1,000 47 13 10 FIT-5 1, 000 1. 000 1,000 1,000 1, 000 (ET-5 plus 10 p.p.m. H102) 1,000 1,000 1,000 l, 000

(In fresh water) H2O 1.000 1, 000 1,000 1,000 1,000 (Duomeen T diacetate) 1, 000 1 3 (Duomeen T Diacetate plus 10 p.p.m. H 02)" 15 0 0 0 Arquad T-2O 1.000 150 15 15 (Arquad T2C plus 10 p.p.m. H 02) 1,000 0 1 0 AFTER 10 MINUTES (In the Burbank produced well water) 13 H701" 1,000 1, 000 1,000 1, 000 1, 000 14 Phenol 1,000 1, 000 1,000 1,000 1,000 15 Phenol plus 10 p.p.m. H201" 1,000 1,000 1,000 1,000 1,000 16 Tris phenol 1,000 1, 000 1, 000 75 13 17 Tris phenol plus 10 p.p.m. H202 150 27 6 4 7 18 T-5 1, 000 1, 000 1. 000 1, 000 1,000 19 ET-5 plus 10 p.p.m. H102 1, 000 1,000 1,000 150 1 (In fresh water) 13 0- 1,000 1,000 1,000 1, 000 Duomeen 'I diacetate 1 0 atom, and acetate salts of saturated acyclic amines, in which the alkyl and the acyclic radicals have from to 20 carbon atoms each.

AFTER MINUTES (In the Burbank produced well water) H202 1,000 1,000 1,000 1, 000 150 Ph arm] 1, 000 1, 000 1, 000 1, 000 1, 000 Phenol plus 10 p.p.m. H102 1, 000 1, 000 1, 000 1, 000 1, 000 Tris phenol 1, 000 1, 000 150 50 17 Tris phenol plus 10 pm. H20 23 15 O 2 0 ET-5 1, 000 1, 000' 1, 000 1, 000 100 ET-5 plus 10 p.p.m. H202 1, 000 1, 000 100 8 o (In fresh water) 32 H202 1,000 1,000 1, 000 1,000 33 Duomeen T diacetate 0 0 2 1 34 .-Y Duomeen T diacetate plus 10 p.p.m. 11202.--. 0 0 O 35 Arquad T-2C 10 36 Arquad T-2O plus 10 p.p.m. H202 0 0 0 AFTER MINUTES (In the Burbank produced well water) H20 1,000 1, 000 1, 000 1, 000 9 Pha'nnl 1,000 1, 000 1, 000 1, 000 1, 000 Phenol plus 10 p.p.m. H202 1, 000 1, 000 1, 000 1, 000 1, 000 Tris phenol 100 75 40 23 12 Tris phenol plus 10 p.p.m. Hz0 1 0 0 0 0 ET-5 1, 000 1, 000 150 100 28 ET-5 plus 10 p.p.m. H2O; 150 100 0 O 0 1,000 1,000 1, 000 1, 000 1, 000 F plus 10 p.p.m. H202 1, 000 1, 000 1, 000 150 v 150 Believed caused by later accidental contamination.

In the above Table III, the count is the number of 2. A bactericidal liquid resistant to the formation of colonies of bacteria, each containing one to as many as 30 colonies of anaerobic bacteria, comprising a major amount would be in a control tube with no bactericide treatment of water, and in parts per million of the volume of said at which would be about 13000 to 3,000 Organisms, as Water, 2.5 to 20 p.p.m. of an aqueous solution of 29% by counted w th the usual bacteria colony counter. Where i h h d id d 25 20 f a the Count 13 1,000 It 111621515 99 or q quaternary diacetate salt of a tallow primary amine.

In th 81 Table 2 2 chemically p f 3. A bactericidal liquid resistant to the formation of aqueous solbmon of 29% by s gi h g gig colonies of anaerobic bacteria, comprising a major amount f%% gf g, i gi f m m #5:; g; of water, and in parts per million or" the volume of said T 15 y ene omp e water, 2.5 to 20 p.p.m. of an aqueous solution of 29% T diacetate 1s a diacetate salt of a tallow primary amine, b Wei ht h dw en eroxide and 2 5 to 20 of Arquad T-2C is a 1 to 1 mixture of tallow trimethyl g y g p a ammonium chloride and dHOCOmH dimethyl ammonium mixture of one part tallow trimethyl ammonium chlorlde chloride as a 50% solution in propanol-Z (said propanol and one dl'coconut dlmethyl f chlonde g inert as a bactericide as employed), and is both combined as a 50% solution m an inert solvent, sodium pentachlorophenate 34% solution in ethylene P 9 'treatlllg a Well l g P p V glycol id l l h i no b i id l efle t as down said well into the permeable earth formations there- 1 d) in, the composition of claim 1.

In runs 1, 8, 13, 20, 25, 32, and 37 the amounts of 5. The process of treating a well comprising pumping hydrogen peroxide varied from 2.5 to 20 p.p.m. as indown said well into the permeable earth formations theredicated at the head of the respective column, but in in, the composition of claim 2. all other runs containing hydrogen peroxide as indicated 6. The process of treating a well comprising pumping y had 10 P-P- Whlle the Other bactellclde Famed down said well into the permeable earth formations therefrom i0 PP- in, the composition of claim 3.

Wh11e certam compounds have been named and certain data given for purposes of illustration, the invention ob- 55 References Cited in the file of thi patent 'viously is not limited thereto.

Having described my invention, I claim: UNITED STATES PATENTS 1. A bactericidal liquid resistant to the formationof 3 Krallse Jan. 18, 1938 colonies of anaerobic bacteria, comprising a major amount ,375,854 Kirby May 15, 1945 of water, and in parts per million of the volume of said 2,420,099 Salle et a1. May 6, 1947 water, 2.5 to 20 p.p.m. of an aqueous solution of 29% 2,692,231 Stayner et 1. O t, 19, 1954. by weight hydrogen peroxide and 2.5 to 20 P-P-Im f a 2,798,046 Beaver et a1. July 2, 1957 amine bactericide selected from the group consisting of water dispersible and water soluble saturated completely FOREIGN PATENTS acyclic tetraalkyl quaternary ammonium halide salts in 604,277 Great Britain July 1, 1948 which the alkyl groups are all attached to the nitrogen OTHER REFERENCES Wadley: The Evid. Required to Show Synergistic Action of Insect and a Short Cut in Analysis, USDA, June 1955. 

1. A BACTERICIDAL LIQUID RESISTANT TO THE FORMATION OF COLONIES OF ANAEROBIC BACTERIA COMPRISING A MAJOR AMOUNT OF WATER, AND IN PARTS PER MILLION F THE VOLUME OF SAID WATER, 2.5 TO 20 P.P.M. OF AN AQUEOUS SOLUTION OF 29% BY WEIGHT HYDROGEN PEROXIDE AND 2.5 TO 20 P.P.M. OF AN AMINE BACTERICIDE SELECTED FROM THE GROUP CONSISTING OF WATER DISPERSIBLE AND WATER SOLUBLE SATURATED COMPLETELY ACYCLIC TETRAALKYL QUATERNARY AMMONIUM HALIDE SALTS IN WHICH THE ALKYL GROUPS ARE ALL ATTACHED TO THE NITROGEN ATOM, AND ACETATE SALTS OF SATURATED ACYLIC AMINES, IN WHICH THE ALKYL AND THE ACYCLIC RADICALS HAVE FROM 5 TO 20 CARBON ATOMS EACH. 